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Universidade Federal De Santa Catarina Centro Tecnológico Programa De Pós-Graduação Em Engenharia Ambiental UNIVERSIDADE FEDERAL DE SANTA CATARINA CENTRO TECNOLÓGICO PROGRAMA DE PÓS-GRADUAÇÃO EM ENGENHARIA AMBIENTAL CAROLINE RODRIGUES TRATAMENTOS DE ÁGUA FLUVIAL CONTAMINADA COM DRENAGEM ÁCIDA DE MINERAÇÃO (DAM) VISANDO A REMOÇÃO DE SULFATO: BIOESTIMULAÇÃO DE BACTÉRIAS REDUTORAS DE SULFATO E ELETROCOAGULAÇÃO FLORIANÓPOLIS 2020 CAROLINE RODRIGUES TRATAMENTOS DE ÁGUA FLUVIAL CONTAMINADA COM DRENAGEM ÁCIDA DE MINERAÇÃO (DAM) VISANDO A REMOÇÃO DE SULFATO: BIOESTIMULAÇÃO DE BACTÉRIAS REDUTORAS DE SULFATO E ELETROCOAGULAÇÃO Tese submetida ao Programa de Pós-Graduação em Engenharia Ambiental da Universidade Federal de Santa Catarina, como parte dos requisitos para obtenção do título de Doutor em Engenharia Ambiental. Orientação: Drª María Ángeles Lobo Recio Coorientação: Dr. Flávio R. Lapolli FLORIANÓPOLIS 2020 CAROLINE RODRIGUES Tratamentos de água fluvial contaminada com drenagem ácida de mineração (DAM) visando a remoção de sulfato: bioestimulação de bactérias redutoras de sulfato e eletrocoagulação O presente trabalho em nível de doutorado foi avaliado e aprovado por banca examinadora composta pelos seguintes membros: Profª. Lucila Adriani Coral, Drª. Universidade Tecnológica Federal do Paraná Profª. Regina Vasconcellos Antonio, Drª. Universidade Federal de Santa Catarina (Campus Araranguá) Profª. Maria Eliza Nagel Hassemer, Drª. Universidade Federal de Santa Catarina Certificamos que esta é a versão original e final do trabalho de conclusão que foi julgado adequado para obtenção do título de doutor em Engenharia Ambiental. ____________________________ Profª. Maria Eliza Nagel Hassemer, Drª Coordenadora do Programa de Pós-Graduação em Engenharia Ambiental ____________________________ Profª. María Ángeles Lobo Recio, Drª. Orientadora Florianópolis, 2020. AGRADECIMENTOS Agradeço à minha orientadora, professora María Ángeles por ter depositado sua confiança em mim durante esta jornada, juntamente ao professor Flávio Lapolli, meu coorientador e supervisor do LaRA (Laboratório de Reuso de Águas), por sempre prover o necessário à nossa pesquisa. À professora Maria Eliza, também integrante do LaRA, pela amizade, além de companhia nas confusões na viagem à Austrália. Agradeço à toda minha família, em especial ao meu lar nº 1: meus pais Marco e Carmem, e minhas irmãs Natália e Brígida, que souberam me ensinar respeitáveis valores que me conduziram até aqui. E também ao meu pequeno grande amorzinho, meu sobrinho João Marco. Aos meus queridos avôs Ruth, Alfredo e Jacy. À minha linda tia Fátima, exemplo de superação diária. E a todos os outros familiares, que direta ou indiretamente me ajudaram a trilhar meus caminhos. Todo meu amor a vocês! Ao meu namorado Lucas Postal, pela paciência, compreensão, amor, apoio e toda parceria nesta jornada. Com certeza essa caminhada ao teu lado foi muito mais leve! <3 Aos grandes amigos e parceiros que fiz no LaRA: Tiago, Rady, Pauline, Jossy, Lucila, Dámaris, Ronaldo, Fernanda, Marcelo, Marie, Cris Folzke, André, Hioná, Ana Karla, Mauana, Vlade, Thamires, Rubia, Emerson, Ana Silvia, Beatriz, Raphael e tantos outros... Alguns já se foram do lab, outros ainda permanecem, certamente todos estão em meu coração, mas com certeza alguns vou levar para a vida! Obrigada! À nova e velha guarda do PPGEA: Lorena (diretamente da graduação no IBILCE), Jamile, Wanderli, Bruna, Isa, Beda, Ju Muller, Fran, Karina, Tiago Vitor, Hugo, Cassio, Cris de Léis, Edi, Jéssica, Maria Joana, Henrique, Claudinha, Naiara Ramos, Cris Lalau. Obrigada pelas risadas, rolêzinhos, festinhas da UFSC, praias, trilhas, voleizinhos no sábado à tarde e encontros gastronômicos. Hoje diversos são professores, uns estão espalhados pelo Brasil e também pelo mundo: tenho muito orgulho de ter feito parte da jornada de cada um de vocês aqui em Floripa! Aos demais amigos que fiz nessa Ilha da Magia, em especial a Rodrigo, Jéssica, Isaac e Dani Hock. Às minhas colegas de apê que tive em Floripa, em especial à Marina, Lari e Renata, que além de dividirmos o teto e as contas a pagar (que por sinal não eram poucas), também dividimos muitas risadas e momentos de reflexão. Aos membros da banca avaliadora, professoras Regina, Lucila e Maria Eliza, pela disponibilidade e auxílio no aprimoramento deste trabalho. Além do LaRA, agradeço também ao PPGEA, ao Dep. Eng. Sanitária e Ambiental, ao LIMA (Lab. Integrado do Meio Ambiente), ao Laboratório de Toxicologia Ambiental (LABTOX), e às duas agências de fomento à pesquisa: CAPES, pela concessão de bolsa doutorado e ao CNPq, pelo projeto CT-Mineral, pois o conjunto de todos estes viabilizaram a realização da minha pesquisa de doutorado. Ao LED (Laboratório de Educação Digital), que possibilitou a defesa por videoconferência, pois devido à pandemia do COVID-19, houve suspensão de todas as atividades presenciais na Universidade. E por último, mas não menos importante, às bolsistas de IC Bruna Ritzmann e Mônica Vitart, pelo exemplar auxílio no laboratório e por serem sempre responsáveis e muito solícitas às demandas, e também aos (agora ex-) servidores Elaine (LIMA), Gustavo e Jorge (secretaria ENS). Fechando-se este ciclo, que não foi fácil, mas também não impossível, sou grata inclusive aos momentos difíceis que passei, pois tem um ditado que profere que nunca perdemos: nós ganhamos ou aprendemos. Portanto, posso dizer que aprendi e cresci bastante com todos eles! “If we knew what we are doing, it would not be called research would it?” Albert Einstein RESUMO A atividade de mineração de carvão possui grande importância histórica e econômica para o estado de Santa Catarina. Entretanto, estima-se que haja em torno de mil minas abandonadas no estado, e por conta disto, a Bacia Carbonífera Catarinense é altamente impactada, pois mesmo abandonadas, estas minas continuam liberando Drenagem Ácida de Mineração (DAM). Desta forma, diversos rios e mananciais desta região são considerados mortos, por se tratar de 2- um efluente extremamente tóxico, visto que além de ser ácido e rico em sulfato (SO4 ), a DAM apresenta elevada concentração de metais dissolvidos. A presente pesquisa visou a remediação de água de rio impactada por DAM (AIDAM) focando na remoção de sulfato, sendo utilizadas duas vertentes: a bioestimulação das Bactérias Redutoras de Sulfato (BRS), e a eletrocoagulação (EC), ambas no tratamento da AIDAM oriunda do rio Sangão. No tratamento biológico, foram construídos microcosmos livres de oxigênio usando como fontes de carbono: quitina comercial (QUIT) e casca de camarão (CC). Variaram-se também outras condições de operação: adição ou não de inóculo, remoção prévia dos íons metálicos da AIDAM, adição de carbonato. Todos os ensaios efetuados com CC apresentaram sulfato-redução. Nestes ensaios 3+ foram avaliadas as cinéticas da remoção de sulfato e íons metálicos (Fet, Al e Mnt), bem como a análise da comunidade microbiana através da técnica de sequenciamento high throughput. Excelentes remoções de poluentes foram obtidas após 41 dias de tratamento nos diferentes ensaios realizados utilizando CC como substrato, e embora tenham-se detectado BRS (gêneros Desulfosporosinus e Desulfovibrio), em nenhum dos casos as BRS representaram a maioria, apresentando abundância relativa em torno de 1% ou menos; já as bactérias fermentadoras, anaeróbias facultativas, produtoras de quitinase e/ou ligadas à atividade sulfato-redutora (gêneros Clostridium, Klebsiella, Citrobacter e Klebsiella) predominaram. No ensaio com AIDAM livre de íons metálicos e CC, predominou o gênero Comamonas, e muito brandamente detectou-se Desulfovibrio. Concluiu-se com estes resultados, que a sulfato-redução esteve mais ligada à matéria orgânica disponível às BRS que a sua abundância, provavelmente porque as bactérias fermentadoras e produtoras de quitinase são as responsáveis por quebrar a estrutura complexa da quitina, deixando o substrato disponível para as BRS, através de uma relação de sinergia entre o consórcio microbiano. Para os ensaios utilizando QUIT como fonte carbônica, nenhum deles apresentou atividade sulfato-redutora, nem mesmo com correção de pH com carbonato, evidenciando que apenas a quitina não é substrato adequado para o desenvolvimento das BRS. Em consequência, deduz-se que a característica de substrato adequado para a sulfato- redução apresentada pela CC seja provavelmente devida a sua composição (quitina + proteínas + minerais). Nos ensaios de eletrocoagulação, foram testadas diferentes densidades de corrente (35, 50 e 65 A∙m-2) e modos de exposição à corrente elétrica (intermitente ou contínuo), e juntamente a estes dados, foi realizado um planejamento fatorial 2², no intuito de convergir para 2- a melhor condição na remoção de SO4 . Após 5 horas de ensaio, a densidade de corrente de 65 A∙m-2 em modo de exposição contínuo mostrou-se a melhor condição, proporcionando 2- eficiência de 70,95% na remoção de SO4 , seguindo uma cinética de decaimento de terceira ordem. Para fins de comparação, e visando um possível uso não potável da água tratada, foram efetuados ensaios toxicológicos com Landoltia punctata para os efluentes resultantes dos tratamentos biológico e eletroquímico de AIDAM. Os resultados obtidos mostraram baixa toxicidade do efluente após eletrocoagulação e, em contrapartida, elevada toxicidade do resultante após ensaio biológico, provavelmente devido à presença de sulfeto de hidrogênio. Este resultado, aliado ao fato de o efluente possuir odor, impede a possibilidade de seu uso secundário não-potável, elevando, portanto, o tratamento por eletrocoagulação como a opção mais viável de tratamento testada neste trabalho para a remoção
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